Frustrated amino functional group coupling with electric field makes CO 2 activation easier.

New models associated with frustrated geometry and an external electric field (EEF) were designed to qualitatively and quantitatively explore CO 2 activation through density functional calculations. We investigated the influence on CO 2 of the microenvironments of methylamine (CH 3 NH 2 ) positioned at different heights above a Cu (111) surface in the presence and absence of an electric field. The results demonstrate that at an approximate distance of 4 ± 1 Å between N and the metal surface, neither lower nor higher, under an EEF over 0.4 V Å -1 , there is a remarkable synergistic effect between the chemical interaction and EEF that activates CO 2 , and also lowers the required EEF strength. This is in contrast to the separate factors or any other combinations of them which do not achieve the synergistic effect. In addition, when H in was replaced by F, the O-C-O angle of CO 2 is not affected. This phenomenon further illustrates that the synergistic effect is very sensitive to the nucleophilicity of NH 2 . Various other chemical groups and substrates were investigated, and PHCH 3 also displays a distinctive chemisorption CO 2 state. The substrate also plays a significant role, except that Au cannot generate a similar effect. Furthermore, constraining or facilitating CO 2 activation strongly depends on the distance between the chemical group and the substrate. Appropriate combinations of the three factors related to the substrate Cu, the chemical group CH 3 NH 2 and the EEF provide new protocols to make CO 2 activation easier and controllable.